JP6403080B1 - Coating composition and method for producing coating film - Google Patents

Abstract

Disclosed is a coating composition that can be cured at room temperature, and a coating film that is obtained from the coating composition and that is excellent in appearance and non-adhesiveness before and after rubbing. A coating composition includes a first oligomer containing a dialkylsiloxane unit, an alkoxy group-containing siloxane unit containing an alkoxy group, and an alkoxy group-containing siloxane containing no alkoxy group and not containing a dialkylsiloxane unit. A second oligomer containing a unit, silicone oil, a catalyst, and an organic solvent are contained. The ratio of the total amount of the first oligomer and the second oligomer to the coating composition is 20% by mass or more and 50% by mass or less. The ratio of the first oligomer to the second oligomer is 0.15 or more and 10 or less. The kinematic viscosity at 25 ° C. of the silicone oil is 100 mm 2 / s or more. The catalyst is at least one selected from the group consisting of metal alkoxides, metal chelate compounds, and metal carboxylates. The vapor pressure of the organic solvent at 20 ° C. is 1 kPa or more. [Selection figure] None

Description

  The present invention relates to a coating composition and a coating film, and more particularly to a coating composition and a coating film which is a cured product thereof.

  Conventionally, it is known to form non-adhesiveness on various products by forming a coating film made of silicone resin on the surface of the various products.

  For example, it has been proposed to apply a coating composition containing a first oligomer, a second oligomer, and a silicone oil and substantially not containing a solvent to a product that requires non-tackiness ( For example, see Patent Document 1.)

  The coating composition described in Patent Document 1 is applied to a product, then heat-treated and cured to form a coating film.

JP 2017-82207 A

  However, after the coating composition is applied to the product, it may not be heat-treated depending on the application. Therefore, when the coating composition described in Patent Document 1 is not heat-treated, there is a problem that the curing becomes insufficient and a coating film cannot be formed.

  The coating film is required to have an excellent appearance (aesthetic appearance).

  Furthermore, the coating film may be rubbed, and excellent non-adhesiveness before and after that is also required.

  An object of the present invention is to provide a coating composition that can be cured at room temperature, and a cured film that is excellent in appearance and non-adhesiveness before and after rubbing.

The present invention (1) includes a first oligomer containing a dialkylsiloxane unit, an alkoxy group-containing siloxane unit containing an alkoxy group, and an alkoxy group-containing siloxane unit containing no alkoxy group but containing an alkoxy group. A coating composition containing a second oligomer to be contained, silicone oil, a catalyst, and an organic solvent, wherein a ratio of the total amount of the first oligomer and the second oligomer to the coating composition is 20 masses. % To 50% by mass, the ratio of the first oligomer to the second oligomer is 0.15 to 10, and the kinematic viscosity of the silicone oil at 25 ° C. is 100 mm ² / s or more. And the catalyst comprises a metal alkoxide, a metal chelate compound, and a metal carbonate. Is at least one selected from the group consisting of phosphate salts, the vapor pressure at 20 ° C. of the organic solvent is 1kPa or more, comprising the coating composition.

  The present invention (2) includes the coating composition according to (1), wherein the organic solvent is an alcohol solvent.

  In the present invention (3), the ratio of the organic solvent to the total amount of 100 parts by mass of the first oligomer, the second oligomer and the silicone oil is 40 parts by mass or more and 300 parts by mass or less. Or the coating composition as described in (2) is included.

  In the present invention (4), the ratio of the catalyst to the total amount of 100 parts by mass of the first oligomer and the second oligomer is 2 parts by mass or more and 55 parts by mass or less. The coating composition as described in any one is included.

  This invention (5) contains the coating film which is a hardened | cured material of the coating composition as described in any one of (1)-(4).

  The coating composition of the present invention contains a first oligomer, a second oligomer, a catalyst, and an organic solvent, the ratio of the total amount of the first oligomer and the second oligomer is 20% by mass or more, and the catalyst is a metal alkoxide, It is at least one selected from the group consisting of metal chelate compounds and metal carboxylates, and the vapor pressure of the organic solvent at 20 ° C. is 1 kPa or more. Therefore, the coating composition can be cured at room temperature. As a result, this coating composition can be used for applications that do not require heat treatment.

The coating composition of the present invention contains silicone oil, and the kinematic viscosity at 25 ° C. of the silicone oil is 100 mm ² / s or more. Therefore, the coating film which is a cured product of the coating composition is excellent in non-stickiness before and after rubbing.

  Furthermore, in the coating composition of this invention, since the ratio of the 1st oligomer with respect to the 2nd oligomer is 0.15 or more and 10 or less, it is excellent in the non-adhesiveness after the coating film is rubbed.

  Moreover, in the coating composition of this invention, the ratio of the total amount of a 1st oligomer and a 2nd oligomer is 50 mass% or less. Therefore, the coating composition is excellent in application workability. As a result, the coating film that is a cured product of the coating composition is excellent in appearance.

  The coating composition of the present invention is a room temperature curable coating composition (substantially synonymous with room temperature curable type), and forms a coating film that is a cured product by room temperature curing. The normal temperature is a temperature at which heating (specifically, heating at 50 ° C. or higher) is not performed when a coating film is formed from the coating composition, for example, less than 50 ° C., preferably 40 ° C. or lower. Yes, for example, 0 ° C. or higher, preferably 10 ° C. or higher.

  The coating composition contains a first oligomer, a second oligomer, a silicone oil, a catalyst, and an organic solvent.

  The first oligomer forms a siloxane matrix together with the second oligomer in the coating film, and is a non-sticking auxiliary agent that assists the non-stickiness and water repellency of silicone oil in the coating film even when the coating film is rubbed. . Thereby, the coating film can effectively suppress a non-adhesive decrease after a long period of time.

  The first oligomer contains a dialkylsiloxane unit and an alkoxy group-containing siloxane unit containing an alkoxy group.

  Specifically, the first oligomer is a siloxane oligomer represented by the following formula (1).

  Formula (1):

(In the formula, R ^{1 to} R ⁹ may be the same or different from each other, and are at least one monovalent hydrocarbon selected from the group consisting of a monovalent saturated hydrocarbon group and a monovalent aromatic hydrocarbon group. X represents a siloxane unit, a and e may be the same or different from each other, and are 1 or 2. b is an integer of 2 or more and 20 or less, and c is 2 or more. (It is an integer of 10 or less, and d is an integer of 2 or more and 20 or less.)
Examples of the monovalent saturated hydrocarbon group represented by R ^{1 to} R ⁹ include methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, n- C1-C6 alkyl groups, such as pentyl and n-hexyl, are mentioned, Preferably, methyl is mentioned.

Examples of the monovalent aromatic hydrocarbon group represented by R ^{1 to} R ⁹ include aryl groups having 6 to 10 carbon atoms such as phenyl and naphthyl, and preferably include phenyl.

That is, as R < ¹ > -R < ⁹ >, Preferably, methyl and / or phenyl are mentioned, More preferably, methyl is mentioned.

In the first oligomer, the unit I is an alkoxy group-containing siloxane unit. That is, the unit I contains an alkoxy group represented by R ² O.

a represents the number of alkoxy groups represented by R ² O— which are bonded to the silicon atom in the unit I, and is preferably 2. In that case, in the unit I, the number (3-a) of monovalent hydrocarbon groups represented by R ¹ bonded to the silicon atom is preferably 1 (= 3-2).

  In the unit I, the oxygen atom in Si—O— is bonded to any silicon atom among the units II to IV described below. Thereby, Si-O- of this unit I constitutes a siloxane bond in the first oligomer.

  Unit I is a molecular terminal unit in the first oligomer.

Unit II is an alkoxy group-containing siloxane unit. That is, the unit II contains an alkoxy group represented by R ⁴ O.

  b means the number of units II. b is preferably an integer of 3 or more, preferably 13 or less.

  Unit III is a siloxane unit having two oxygen atoms bonded to a silicon atom. Unit III may contain an alkoxy group.

  Examples of the siloxane unit represented by X include unit VI (described later) alone, a combination of unit II and unit I, a combination of unit II and unit V, and a combination of unit II and unit VI (described later).

  Examples of X include a cyclic siloxane unit represented by the following formula (2).

  Formula (2):

(In the formula, m is an integer of 2 or more. Z ¹ is the above-described monovalent hydrocarbon group or alkoxy group.)
Examples of the monovalent hydrocarbon group represented by Z ^1, preferably, methyl. Examples of the monovalent alkoxy groups represented by Z ^1, preferably, include methoxy.

  c means the number of units III. c is preferably an integer of 6 or less.

Unit IV is a dialkylsiloxane unit. That is, unit IV contains an alkyl group represented by R ⁶ and R ⁷ .

  d means the number of units IV. d is preferably an integer of 6 or less.

Unit V is an alkoxy group-containing siloxane unit. That is, the unit V contains an alkoxy group represented by R ⁹ O.

  The silicon atom in the unit V is bonded to any oxygen atom in the units II to IV. Thereby, the silicon atom in the unit V forms a siloxane bond in the first oligomer.

  Unit V is a molecular terminal unit in the first oligomer.

e represents the number of alkoxy groups represented by R ⁹ O— which are bonded to a silicon atom in the unit V, and is preferably 2. In that case, in the unit V, the number (3-e) of monovalent hydrocarbon groups represented by R ⁸ bonded to the silicon atom is preferably 1 (= 3-2).

Each of the above-mentioned units and the number thereof are specified by ¹ H-NMR and ²⁹ Si-NMR.

Moreover, a 1st oligomer can also be shown by the following average compositional formula (A).
Average composition formula (A):
R ^p _α Si (OR ^q ) _β O _(4-α-β) (A)
(In the formula, R ^p and R ^q may be the same or different from each other, and represent a monovalent hydrocarbon group. Α is a value having an average value in the range of 0.40 to 1.70. Β represents a value at which the ratio of OR ^q bonded to the silicon atom in the average composition formula (A) is 5% by mass or more and less than 40% by mass.)
The monovalent hydrocarbon group is the same as the above-described monovalent hydrocarbon group.

In the average composition formula (A), R ^p is a monovalent hydrocarbon group similar to R ¹ , R ³ , R ⁵ , R ⁶ , R ⁷ , R ⁸ in the general formula (1). Examples of R ^q include the same monovalent hydrocarbon groups as R ² , R ⁴ , and R ⁹ in the above general formula (1).

Β in the average composition formula (A) is such that the ratio of OR ^q bonded to the silicon atom in the average composition formula (A) is, for example, 10% by mass or more, preferably 20% by mass or more. , 35% by mass or less, preferably 30% by mass or less.

  Specifically, the first oligomer contains, for example, a methyl silicone alkoxy oligomer containing a dimethylsiloxane unit and a methoxy group-containing siloxane unit, a methylphenylsiloxane unit, and a siloxane unit containing a methoxy group and a phenoxy group. Methylphenyl silicone alkoxy oligomers, and the like, preferably methyl silicone alkoxy oligomers.

Methyl silicone alkoxy oligomer
For example, it is represented by the following formula (3).

  Formula (3):

(Wherein b to d and X are the same as b to d and X in formula (1)).
Such a methyl silicone alkoxy oligomer is produced from, for example, methyltrimethoxysilane and dimethyldimethoxysilane.

  The molecular weight of the first oligomer is, for example, 500 or more, preferably 1000 or more, and for example, 3000 or less, preferably 2000 or less.

  As the first oligomer, a commercially available product is used. For example, X-40-9250 (in formula (3), b is 8, methyl is 4 and d is 4, a methyl silicone alkoxy oligomer, manufactured by Shin-Etsu Chemical Co., Ltd.) Etc. are used.

  The proportion of the first oligomer is, for example, 1% by mass or more, preferably 2% by mass or more, more preferably 3% by mass or more, still more preferably 5% by mass or more, particularly preferably relative to the coating composition. 6 mass% or more, and for example, less than 50 mass%, preferably 45 mass% or less, more preferably 40 mass% or less, still more preferably 30 mass% or less, and particularly preferably 20 mass%. Hereinafter, it is most preferably 10% by mass or less.

  The second oligomer forms a siloxane matrix with the first oligomer in the coating film.

  The second oligomer does not contain a dialkylsiloxane unit but contains an alkoxy group-containing siloxane unit.

  Specifically, the second oligomer is a siloxane oligomer represented by the following formula (4).

  Formula (4):

(In the formula, R ^{11 to} R ¹⁷ may be the same or different from each other, and at least one monovalent hydrocarbon selected from the group consisting of a monovalent saturated hydrocarbon group and a monovalent aromatic hydrocarbon group) Y represents a siloxane unit, and f and i may be the same or different from each other, and are 1 or 2. g is an integer of 2 or more and 20 or less, and h is 2 or more. , An integer of 18 or less.)
Examples of the monovalent saturated hydrocarbon group represented by R ^{11 to} R ¹⁷ include methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, n- C1-C6 alkyl groups, such as pentyl and n-hexyl, are mentioned, Preferably, methyl is mentioned.

Examples of the monovalent aromatic hydrocarbon group represented by R ^{11 to} R ¹⁷ include aryl groups having 6 to 10 carbon atoms such as phenyl and naphthyl, and preferably include phenyl.

That is, as R < ¹¹ > -R < ¹⁷ >, Preferably, methyl and / or phenyl are mentioned, More preferably, methyl is mentioned.

In the second oligomer, the unit XI is an alkoxy group-containing siloxane unit. That is, the unit XI contains an alkoxy group represented by R ¹² O.

f represents the number of alkoxy groups represented by R ¹² O— bonded to a silicon atom in the unit XI, and is preferably 2. In that case, in the unit XI, the number (3-f) of monovalent hydrocarbon groups represented by R ¹¹ bonded to the silicon atom is preferably 1 (= 3-2).

  The oxygen atom in the unit XI is bonded to the silicon atom of the unit XII or unit XIII described below. Thereby, Si-O- of this unit XI constitutes a siloxane bond in the second oligomer.

  Unit XI is a molecular terminal unit in the second oligomer.

Unit XII is an alkoxy group-containing siloxane unit. That is, the unit XII contains an alkoxy group represented by R ¹⁴ O.

  g means the number of units XII. g is preferably an integer of 3 or more, preferably 17 or less.

  Unit XIII is a siloxane unit having two oxygen atoms bonded to a silicon atom. Unit XIII may contain an alkoxy group.

  Examples of the siloxane unit represented by Y include unit XVI (described later) alone, a combination of unit XII and unit XI, a combination of unit XII and unit XIV, and a combination of unit XII and unit XVI (described later).

  Examples of Y include a cyclic siloxane unit represented by the following formula (5).

  Formula (5):

(In the formula, j is an integer of 2 or more. Z ² is the above-described monovalent hydrocarbon group or alkoxy group.)
Examples of the monovalent hydrocarbon group represented by Z ^2, preferably, methyl. Examples of the monovalent alkoxy groups represented by Z ^2, preferably, include methoxy.

  h means the number of units XIII. h is preferably an integer of 3 or more, preferably 15 or less.

  The silicon atom in unit XIV is bonded to the oxygen atom in unit XII or unit XIII. Thereby, the silicon atom in the unit XIV forms a siloxane bond in the second oligomer.

  Unit XIV is a molecular terminal unit in the second oligomer.

i means the number of alkoxy groups represented by R ¹⁷ O— bonded to a silicon atom in the unit XIV, and is preferably 2. In that case, in the unit XIV, the number (3-i) of monovalent hydrocarbon groups represented by R ¹⁶ bonded to the silicon atom is preferably 1 (= 3-2).

Each of the above-mentioned units and the number thereof are specified by ¹ H-NMR and ²⁹ Si-NMR.

Moreover, a 2nd oligomer can also be shown by the following average compositional formula (B).
Average composition formula (B):
R ^t _γ Si (OR ^s ) _δ O _(4-γ-δ) (B)
(In the formula, R ^t and R ^s may be the same or different from each other, and represent a monovalent hydrocarbon group. Γ is a value whose average value is in the range of 0.40 to 1.70. Δ represents a value at which the ratio of OR ^s bonded to silicon atoms in the average composition formula (B) is 5% by mass or more and less than 40% by mass.)
In the average composition formula (B), as the ^{R t,} the above-mentioned general formula (4) ^in, is ^{R 11, R 13, R 15} 1 monovalent hydrocarbon ^group, the same as ^{R 16.} Examples of ^{R s} Includes the same monovalent hydrocarbon group as R ¹² , R ¹⁴ , and R ¹⁷ in the above general formula (4).

Further, δ in the average composition formula (B) is such that the ratio of OR ^s bonded to the silicon atom in the average composition formula (B) is, for example, 10% by mass or more, preferably 20% by mass or more. , 35% by mass or less.

  Specifically, examples of the second oligomer include a methyl silicone alkoxy oligomer and a methyl phenyl silicone alkoxy oligomer, and a methyl silicone alkoxy oligomer is preferable.

  Examples of the methyl silicone alkoxy oligomer include a methyl silicone methoxy oligomer produced from methyl trimethoxysilane.

  The methyl silicone methoxy oligomer is represented, for example, by the following formula (6).

  Formula (6):

(In the formula, g, h and Y are the same as g, h and Y in formula (5).)
Such a methyl silicone alkoxy oligomer is produced from, for example, methyltrimethoxysilane.

  The molecular weight of the second oligomer is, for example, 500 or more, preferably 1000 or more, and for example, 4000 or less, preferably 3000 or less.

  As the second oligomer, a commercially available product is used. For example, KC-89 (manufactured by Shin-Etsu Chemical Co., Ltd.), KR-515 (manufactured by Shin-Etsu Chemical Co., Ltd.), KR-500 (in formula (6), g is 10, h 4 is a methyl silicone alkoxy oligomer produced by Shin-Etsu Chemical Co., Ltd.), X-40-9225 (in formula (6), g is 12 and h is 10 methyl silicone alkoxy oligomer produced by Shin-Etsu Chemical Co., Ltd.) US-SG2403 (manufactured by Toray Dow Corning) or the like is used.

  The proportion of the second oligomer is, for example, 10% by mass or more, preferably 15% by mass or more, more preferably 20% by mass or more, and further preferably 25% by mass or more, based on the coating composition. For example, it is less than 50% by mass, preferably 40% by mass or less, more preferably 35% by mass or less, and still more preferably 30% by mass or less.

  The ratio of the first oligomer to the second oligomer (first oligomer / second oligomer) is 0.15 or more, preferably 0.16 or more, more preferably 0.18 or more, and further preferably 0.20. As mentioned above, More preferably, it is 0.22 or more. The ratio of the first oligomer to the second oligomer is 10 or less, preferably 9 or less, more preferably 7 or less, further preferably 5 or less, particularly preferably 2 or less, and further 1.0. Hereinafter, it is 0.5 or less.

  If the above-mentioned ratio falls below the above-mentioned lower limit or exceeds the above-mentioned upper limit, if the coating film is rubbed, the non-adhesiveness of the silicone oil in the coating film after rubbing can be surely assisted. Therefore, the non-adhesiveness of the coated film after rubbing is reduced. In other words, if the above-mentioned ratio is not less than the above-mentioned lower limit and not more than the above-described upper limit, the non-adhesiveness of the silicone oil in the coated film after rubbing can be reliably assisted, and the coating after rubbing A decrease in non-adhesiveness of the film can be suppressed.

  The ratio of the total amount of the first oligomer and the second oligomer (curing component) to the coating composition is 20% by mass or more, preferably 25% by mass or more, more preferably 30% by mass or more, and further preferably 35% by mass. % Or more.

  If the ratio of the total amount described above does not satisfy the lower limit described above, the ratio of the first oligomer and the second oligomer (curing component) is excessively small, so that a coating film cannot be reliably formed when the curing component is cured at room temperature. In other words, if the ratio of the total amount is equal to or more than the lower limit described above, the ratio of the curing component can be prevented from being excessively reduced, and the curing component can be cured at room temperature to reliably form the coating film. it can.

  The ratio of the total amount of the first oligomer and the second oligomer (curing component) to the coating composition is 50% by mass or less, preferably 45% by mass or less, and more preferably 40% by mass. If the ratio of the total amount described above exceeds the above-described upper limit, workability (applicability) when applying the coating composition decreases, and therefore the appearance of the coating film decreases. In other words, if the ratio of the total amount is equal to or less than the above upper limit, a decrease in applicability is suppressed, and thus the appearance of the coating film is excellent.

Silicone oil is a component that imparts non-stickiness and water repellency to the coating film. Silicone oil has a linear main chain, and has, for example, a polysiloxane repeating structure (-(SiO) _n- ). Examples of the silicone oil include straight silicone oil (unmodified silicone oil) such as polydimethylsiloxane, polymethylphenylsiloxane, and polydiphenylsiloxane. As silicone oil, in addition to straight silicone oil, the main chain ends and / or side chains are modified with alkyl groups, alkenyl groups (including vinyl groups), alkynyl groups, phenyl groups, ionic groups, etc. A silicone oil is also mentioned. Examples of the ionic group include an anionic group such as a mercapto group, and a cationic group such as an amino group.

  These silicone oils can be used alone or in combination of two or more.

  The silicone oil is preferably straight silicone oil, more preferably polydimethylsiloxane.

  As the silicone oil, commercially available products are used. For example, KF-96 series (manufactured by Shin-Etsu Chemical Co., Ltd.), KF-965 series (manufactured by Shin-Etsu Chemical Co., Ltd.), SH200 series (manufactured by Dow Corning Toray), TSF451 series. (Made by Momentive Performance Material Japan), YF-33 series (made by Momentive Performance Material Japan), etc. are used.

The kinematic viscosity at 25 ° C. of the silicone oil is 100 mm ² / s or more, preferably 200 mm ² / s or more, more preferably 500 mm ² / s or more, and most preferably 1000 mm ² / s or more. The kinematic viscosity at 25 ° C. of the silicone oil is, for example, 1 million mm ² / s or less, preferably 500,000 mm ² / s or less, more preferably 100,000 mm ² / s or less, and further preferably 1 It is 10,000 mm ² / s or less.

  If the kinematic viscosity of the silicone oil is below the above lower limit, excellent non-adhesiveness cannot be maintained before and after the coating film is rubbed. In other words, if the kinematic viscosity of the silicone oil is equal to or higher than the lower limit described above, excellent non-adhesiveness can be maintained before and after rubbing the coating film.

  On the other hand, if the kinematic viscosity of the silicone oil is less than or equal to the above upper limit, the silicone oil can be easily handled and the coating composition can be easily prepared.

  The ratio of the silicone oil is, for example, 0.1% by mass or more, preferably 0.5% by mass or more, more preferably 1.0% by mass or more, and further preferably 1.5% by mass or more with respect to the coating composition. For example, it is 10% by mass or less, preferably 5% by mass or less, and more preferably 2.5% by mass or less.

  The number of parts by mass of the silicone oil relative to 100 parts by mass of the first oligomer and the second oligomer is, for example, 1 part by mass or more, preferably 3 parts by mass or more, more preferably 5 parts by mass or more. 20 parts by mass or less, preferably 10 parts by mass or less, more preferably 7 parts by mass or less.

  The ratio of the total amount of the first oligomer, the second oligomer, and the silicone oil to the coating composition is, for example, 21% by mass or more, preferably 26% by mass or more, more preferably 31% by mass or more, and still more preferably, It is 36 mass% or more. If the ratio of the total amount is equal to or more than the above lower limit, it is possible to prevent the ratio of the curing component from being excessively reduced, cure the curing component at room temperature, and reliably form the coating film.

  The ratio of the total amount of the first oligomer, the second oligomer, and the silicone oil to the coating composition is, for example, 51% by mass or less, preferably 46% by mass or less, and more preferably 41% by mass. If the ratio of the total amount described above is equal to or less than the above upper limit, a decrease in applicability is suppressed, and therefore the appearance of the coating film is excellent.

  When the coating composition is cured at room temperature, the catalyst reacts with moisture in the air and hydrolyzes to generate active [metal atom-OH], [metal atom-OH], the first oligomer, and the first oligomer. It is a curing catalyst that causes a condensation reaction between two oligomers.

  The catalyst is at least one selected from the group consisting of metal alkoxides, metal chelate compounds, and metal carboxylates.

  Examples of the metal alkoxide include titanium alkoxide, aluminum alkoxide, zirconium alkoxide (for example, zirconium tetra n-butoxide, zirconium tetra n-propoxide), germanium alkoxide (for example, germanium tetraethoxide), tin alkoxide (for example, tin tetra n). -Butoxide, tin tetra tert-butoxide), hafnium alkoxide (eg, hafnium tetra 2-propoxide, hafnium tetra tert-butoxide), niobium alkoxide (eg, niobium pentaethoxide), tantalum alkoxide (eg, tantalum penta n-butoxide, Tantalum pentaethoxide). Preferably, titanium alkoxide and aluminum alkoxide are used.

  Examples of the titanium alkoxide include titanium trialkoxide and titanium tetraalkoxide, and preferably titanium tetraalkoxide. Examples of the titanium tetraalkoxide include titanium tetramethoxide, titanium tetraethoxide, titanium tetrapropoxide (eg, titanium tetraisopropoxide, titanium tetra n-propoxide), titanium tetrabutoxide (eg, titanium tetraisobutoxide). , Titanium tetra-n-butoxide, etc.), titanium tetrapentoxide, titanium tetrahexoxide, titanium tetra (2-ethylhexoxide) and the like.

  Examples of the aluminum alkoxide include aluminum trialkoxide. Examples of the aluminum trialkoxide include aluminum triethoxide, aluminum tripropoxide (for example, aluminum triisopropoxide, aluminum tri n-propoxide), aluminum tributoxide (for example, aluminum tri sec-butoxide, aluminum tri n- Butoxide) and the like.

  Each of the three or four alkoxy groups in the metal alkoxide has different reactivity depending on the number of carbon atoms and the presence or absence of branching. On the other hand, if the hydrolysis proceeds too quickly, the handleability (stability) may decrease. Therefore, considering reactivity and stability, titanium tetraethoxide, titanium tetraisopropoxide, titanium tetraisobutoxide, and titanium tetra n-butoxide are preferable among titanium alkoxides. Among aluminum alkoxides, aluminum triethoxide, aluminum triisopropoxide, and aluminum trisec-butoxide are preferable.

  As the metal alkoxide, a commercially available product is used, and for example, D-25 (titanium tetra n-butoxide, manufactured by Shin-Etsu Chemical Co., Ltd.) is used.

  Examples of the metal chelate compound include a metal chelate compound having β-diketone, phosphate ester, alkanolamine or the like as a ligand.

  Examples of β-diketones include 2,4-pentanedione, methyl acetoacetate, ethyl acetoacetate, phenyl acetoacetate, 1,3-diphenyl-1,3-propanedione, 2,4-hexanedione, 3,5 -Heptanedione, 2,4-octanedione, 2,4-decanedione, 2,4-tridecanedione, 5,5-dimethyl-2,4-hexanedione, 2,2-dimethyl-3,5-nonanedione, Examples include 2,2,6,6-tetramethyl-3,5-heptanedione, 1,3-cyclopentanedione, 1,3-cyclohexanedione, and the like. Preferably, 2,4-pentanedione is used.

  Examples of octylene glycol include 2-ethyl-3-hydroxyhexoxide.

  Examples of the phosphate ester include 2-ethylhexyl phosphate.

  Examples of the alkanolamine include monoethanolamine, diethanolamine, and triethanolamine.

  As the ligand, β-diketone is preferably used.

  The central metal (metal atom) forming the metal chelate compound is not particularly limited. For example, aluminum, titanium, zirconium, niobium, magnesium, calcium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, Palladium, indium, tin, etc. are mentioned. Preferably, aluminum, titanium, and zirconium are used.

  Specifically, examples of the metal chelate compound include an aluminum chelate compound, a titanium chelate compound, a zirconium chelate compound, a magnesium chelate compound (eg, diaquabis (2,4-pentanedionato) magnesium), a calcium chelate compound (eg, Diaquabis (2,4-pentanedionato) calcium), chromium chelate compounds (for example, tris (2,4-pentanedionato) chromium), manganese chelate compounds (for example, diaquabis (2,4-pentanedionato) ) Manganese), iron chelate compounds (eg, tris (2,4-pentanedionato) iron), cobalt chelate compounds (eg, tris (2,4-pentanedionato) cobalt), nickel chelate compounds (eg, , Bi (2,4-pentanedionato) nickel), copper chelate compounds (for example, bis (2,4-pentandionato) copper), zinc chelate compounds (for example, bis (2,4-pentandionato) zinc) Etc.), tris (2,4-pentanedionato) gallium, etc.), niobium chelate compounds (eg, tetrakis (2,2,6,6-tetramethyl-3,5-heptaneedionatoniobium (IV)) palladium Chelate compounds (for example, bis (2,4-pentanedionato) palladium), indium chelate compounds (for example, tris (2,4-pentandionato) indium), tin chelate compounds (for example, bis (2,4) -Pentandionato) tin etc.).

  Preferred examples of the metal chelate compound include an aluminum chelate compound, a titanium chelate compound, and a zirconium chelate compound. More preferred examples of the metal chelate compound include an aluminum chelate compound and a titanium chelate compound from the viewpoint of maintaining excellent fastness (strength) in the coating film.

  Examples of the aluminum chelate compound include tris (2,4-pentanedionato) aluminum, tris (ethylacetoacetate) aluminum, bis (ethylacetoacetate) (2,4-pentanedionato) aluminum, and the like. Preferably, tris (2,4-pentanedionato) aluminum is used.

  Examples of the titanium chelate compound include tetrakis (2,4-pentanedionato) titanium, tetrakis (ethylacetoacetate) titanium, and the like. Preferably, tetrakis (2,4-pentanedionato) titanium is used.

  Examples of the zirconium chelate compound include tetrakis (2,4-pentanedionato) zirconium and tetrakis (ethylacetoacetate) zirconium. Preferably, tetrakis (2,4-pentanedionato) zirconium is used.

  Moreover, a metal chelate compound contains the alkoxy group containing metal chelate compound which further contains an alkoxy group in addition to an above-described ligand. Examples of the alkoxy group include methoxy, ethoxy, n-propoxy, 2-propoxy, n-butoxy, 2-butoxy and the like. As the alkoxy group, 2-propoxy is preferable. Specifically, as the alkoxy group-containing metal chelate compound, for example, an alkoxy group-containing aluminum chelate compound such as aluminum ethyl acetoacetate diisopropylate, for example, bis (2,4-pentanedionato) bis (2-propanolate) Examples thereof include an alkoxy group-containing titanium chelate compound such as titanium.

  A metal carboxylate is a metal salt of a carboxylic acid.

  Examples of the carboxylic acid include linear carboxylic acids such as ethanoic acid, propanoic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, dodecanoic acid, and tetradecanoic acid. -Branched carboxylic acids such as methylbutanoic acid, 2-methylpentanoic acid, 2-ethylhexanoic acid, 2-methylheptanoic acid, 4-methyloctanoic acid, 3,5,5-trimethylhexanoic acid, such as naphthenic acid And cyclic carboxylic acids. Preferably, branched carboxylic acid is mentioned, More preferably, 2-ethylhexanoic acid is mentioned.

  The metal that forms the metal salt is not particularly limited, and examples thereof include the same metals as the above-described center metal (center metal that forms the metal chelate compound), preferably zinc, iron, cobalt, and manganese. It is done.

  Examples of metal carboxylates include aluminum carboxylate, titanium carboxylate, zirconium carboxylate, niobium carboxylate, magnesium carboxylate, calcium carboxylate, chromium carboxylate, manganese carboxylate, iron carboxylate Acid salts, cobalt carboxylates, nickel carboxylates, copper carboxylates, zinc carboxylates, gallium carboxylates, palladium carboxylates, indium carboxylates, tin carboxylates, tantalum carboxylates, etc. . Preferred examples of the metal carboxylate include zinc carboxylate, iron carboxylate, cobalt carboxylate and manganese carboxylate.

  Examples of the zinc carboxylate include bis (2-ethylhexanoic acid) zinc, zinc acetate, and zinc naphthenate. Preferably, bis (2-ethylhexanoic acid) zinc is mentioned.

  Examples of the iron carboxylate include bis (2-ethylhexanoic acid) iron, iron acetate, and iron naphthenate. Preferably, bis (2-ethylhexanoic acid) iron is used.

  Examples of the cobalt carboxylate include bis (2-ethylhexanoic acid) cobalt, cobalt acetate, and cobalt naphthenate. Preferably, bis (2-ethylhexanoic acid) cobalt is used.

  Examples of the manganese carboxylate include bis (2-ethylhexanoic acid) manganese, manganese acetate, and manganese naphthenate. Preferably, bis (2-ethylhexanoic acid) manganese is used.

  In addition, as a catalyst, acids, such as phosphoric acid and acetic acid, do not produce | generate metal atom -OH, Therefore, OH group based on the alkoxy group of a 1st oligomer and a 2nd oligomer cannot dehydrate-condense. As a result, the curing reaction of the first oligomer and the second oligomer cannot proceed rapidly at room temperature, and the above-described acid is unsuitable as a catalyst.

  The catalyst can be used alone or in combination. As the catalyst, preferably, each of metal alkoxide, metal chelate compound and metal carboxylate is used alone.

  The catalyst may be prepared as a catalyst solution dissolved in an organic solvent described later.

  The ratio of the catalyst is, for example, 0.1% by mass or more, preferably 1% by mass or more, more preferably 5% by mass or more, and for example, 25% by mass with respect to the coating composition. Hereinafter, it is preferably 15% by mass or less.

  The ratio of the catalyst is, for example, 1 part by mass or more, preferably 2 parts by mass or more, more preferably 5 parts by mass or more, and further preferably 10 parts by mass with respect to 100 parts by mass of the total amount of the first oligomer and the second oligomer. It is 20 parts by mass or more, particularly preferably 20 parts by mass or more, and for example, 55 parts by mass or less, preferably 50 parts by mass or less, and more preferably 40 parts by mass or less.

  If the ratio of the catalyst is not less than the above lower limit and not more than the above upper limit, the first oligomer and the second oligomer can be rapidly cured at room temperature to form a coating film at room temperature.

  The organic solvent is a high vapor pressure solvent that is equal to or higher than the lower limit of the vapor pressure described later. Specifically, the high vapor pressure solvent is, for example, an alcohol solvent such as methyl alcohol, ethyl alcohol, isopropyl alcohol (2-propanol), such as ethyl acetate, butyl acetate, methoxybutyl acetate, ethyl glycol acetate, amyl acetate. Ester solvents such as, for example, glycol ether solvents such as ethylene glycol dimethyl ether (high vapor pressure glycol ether solvents), for example, ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, and acetyl acetone, such as n-hexane , N-heptane, n-octane, isooctane and other paraffinic solvents (high vapor pressure paraffinic solvents), for example, cyclopentane, cyclohexane and other naphthenic solvents, benzene, toluene, Emissions, aromatic solvents, such as trimethylbenzene, e.g., benzene, toluene, is selected from an aromatic solvent such as xylene.

  The organic solvent is used alone or in combination of two or more.

  As the organic solvent, an alcohol solvent is preferably selected.

  If the organic solvent is an alcohol solvent, the alkoxy group in the first oligomer and the second oligomer is hydrolyzed in the coating composition before use (coating) (that is, the coating composition in storage (storage)) to cause alcohol. Since the reaction for producing is an equilibrium reaction, it is possible to suppress the production of the above-described alcohol, and therefore, the storage stability of the coating composition is excellent.

  The vapor pressure at 20 ° C. of the organic solvent is 1 kPa (7.5 mmHg) or more, preferably 2 kPa (15 mmHg) or more, more preferably 3 kPa (22.5 mmHg) or more. The vapor pressure of the organic solvent at 20 ° C. is 100 kPa (750 mmHg) or less, preferably 25 kPa (187 mmHg) or less, more preferably 10 kPa (75 mmHg) or less, more preferably 7 kPa (52 mmHg) or less, particularly preferably. 5 kPa (38 mmHg) or less.

  If the vapor pressure of the organic solvent does not satisfy the above lower limit, when the coating composition is cured at room temperature, the organic solvent cannot be rapidly removed (evaporated), and thus a coating film cannot be formed. In other words, when the vapor pressure of the organic solvent is equal to or higher than the lower limit described above, the organic solvent can be quickly removed (evaporated) when the coating composition is cured at room temperature, and thus a coating film can be formed. .

  On the other hand, if the vapor pressure of the organic solvent is not more than the above upper limit, when the coating composition is applied, the organic solvent is prevented from being rapidly removed (distilled), and thus the coating has uneven thickness. Generation | occurrence | production can be suppressed and the coating film which is excellent in an external appearance can be formed.

  On the other hand, the organic solvent is a high vapor pressure solvent, but the low vapor pressure solvent below the lower limit value of the vapor pressure described above can allow a very small amount of contamination that does not impair the effects of the present invention. For example, the low vapor pressure solvent contained in the catalyst solution described above is allowed to be mixed.

  The vapor pressure at 20 ° C. of the low vapor pressure solvent is, for example, less than 1 kPa. Examples of the low vapor pressure solvent include low vapor pressure glycol ether solvents such as diethylene glycol dimethyl ether and diethylene glycol diethyl ether, low vapor pressure paraffin solvents such as mineral terpenes, and petroleum solvents such as mineral spirits. It is done.

  The mixing ratio of the vapor pressure solvent is, for example, 15 parts by mass or less, preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and further preferably 3 parts by mass with respect to 100 parts by mass of the high vapor pressure solvent. Hereinafter, it is particularly preferably 1 part by mass or less. The mixing ratio of the low vapor pressure solvent is, for example, less than 10% by mass, 5% by mass or less, preferably 3% by mass or less, more preferably 1.0% by mass or less, based on the coating composition. Preferably, it is 0.5% by mass or less, and particularly preferably 0.1% by mass or less.

  In addition, although water is not an organic solvent, since the curing reaction of the first oligomer and the second oligomer is too fast, it is an unsuitable aqueous solvent for the coating composition in the present invention.

  The ratio of the organic solvent (high vapor pressure solvent) to the coating composition is, for example, 10% by mass or more, preferably 20% by mass or more, more preferably 30% by mass or more, further preferably 40% by mass or more, and particularly preferably It is 50 mass% or more, for example, 80 mass% or less, Preferably, it is 70 mass% or less, More preferably, it is 60 mass% or less.

  The ratio of the organic solvent to the total amount of 100 parts by mass of the first oligomer, the second oligomer, and the silicone oil is, for example, 40 parts by mass or more, preferably 80 parts by mass or more, more preferably 120 parts by mass or more. Is 140 parts by mass or more, for example, 300 parts by mass or less, preferably 200 parts by mass or less, more preferably 160 parts by mass or less.

  If the ratio of the organic solvent is equal to or higher than the lower limit described above, it is excellent in the handleability of the coating composition and suppresses the generation of coating thickness unevenness due to excessively rapid drying after coating. Can do. On the other hand, if the ratio of the organic solvent is equal to or less than the above upper limit, an excessive decrease in yield can be suppressed.

  In addition, the coating composition can be blended with additives such as pigments at an appropriate ratio according to the use and purpose.

  Examples of the pigment include inorganic pigments and organic pigments, preferably inorganic pigments, and more preferably oxide pigments.

Examples of the oxide pigment include metal oxides such as zinc oxide, aluminum oxide, chromium oxide, titanium oxide (TiO ₂ ), and iron oxide (such as iron oxyhydroxide (FeOOH)). Further, as the metal oxide, _{e.g., CuCr 2 O 4, Cu (} Cr, Mn) 2 O 4, Cu (Fe, Mn) 2 O 4, Co (Fe, Cr) 2 O 4, CoAl 2 O 4, Co ₂ Composite metal oxides such as TiO ₄ are included.

  Examples of the pigment include pearl mica (a pigment obtained by coating natural mica or synthetic mica with a metal oxide such as titanium oxide or tin oxide), aluminum particles, aluminum pieces, silver particles, and silver pieces.

  The pigments can be used alone or in combination. As a pigment, you may use a commercial item, for example.

  The average particle diameter of the pigment is, for example, 0.01 μm or more, preferably 0.1 μm or more, and for example, 500 μm or less, preferably 200 μm or less, more preferably 100 μm or less, and further preferably 10 μm or less. It is.

  The blending amount of the pigment is appropriately determined depending on the color developability and hiding property of the coating film.

  Next, preparation of a coating composition, application thereof, and production of a coating film will be described in order.

  In order to prepare the coating composition, first, the first oligomer, the second oligomer, the silicone oil, the organic solvent, and, if necessary, the additive are blended and mixed in the above-described ratio, and the silicone composition is mixed. To prepare. In addition, when mix | blending a pigment, a pigment is previously disperse | distributed with the organic solvent and it mixes when mix | blending the above.

  Meanwhile, a catalyst is prepared separately.

  Thereby, a silicone composition and a catalyst are prepared as a two-component curable composition.

  Then, a silicone composition and a catalyst are mix | blended in the above-mentioned ratio in the application | coating field, they are mixed, and a coating composition is prepared. In the preparation of the coating composition, the catalyst generates a metal-OH group by hydrolysis.

  Subsequently, the coating composition is applied to the object at the application site.

  The application site includes, for example, a site where heating of the object and the coating composition is restricted, specifically, a factory where the use of fire is restricted.

  Examples of the object include products that require non-tackiness and water repellency. Examples of such an object include a roller, a mold, a resin mold, a plate (plate member), a chute, a hopper, and a cooking utensil.

  Examples of the roller include a drying roller, a coating roller, a transfer roller, a bonding roller, a pressure roller, a guide roller, a roller for applying a pattern to a siding material (outer wall material), a papermaking roller, and a printing roller.

  Examples of molds include hygiene molds, rubber product (tires, gloves, etc.) molds, shoe molds, automotive parts molds, urethane molds, hot melt adhesive molds, solid hot Examples include a melt adhesive extrusion mold.

  Examples of the plate include a plate that is used in a process of bonding a non-woven fabric and a water-absorbing polymer material to which a hot melt adhesive can be attached, a resin pellet sliding plate, and the like.

  Examples of the hopper include a food weighing hopper and a powder charging hopper.

  Examples of cooking utensils include grills, pans, frying pans, and grill dishes.

  Examples of the method for applying the paint to the object include a spray coating method, a bar coating method, a dispenser method, brush coating, and spatula coating. A spray coating method is preferable.

  Subsequently, the coating composition is left together with the object at room temperature at the application site.

  The leaving time is not particularly limited, and is a time during which the organic solvent is distilled off (removed) and the first oligomer and the second oligomer can be cured in the presence of the catalyst. Min. Or more, preferably 1 hour or more, more preferably 10 hours or more, still more preferably 20 hours or more, and 50 hours or less.

  As a result, an OH group is generated from the alkoxy group in the first oligomer and the second oligomer, and it undergoes a dehydration reaction with [metal atom-OH] based on the catalyst, and the curing reaction proceeds.

  Subsequently, the alcohol that is a by-product when the OH group is generated from the alkoxy group of the first oligomer and the second oligomer is removed (evaporated) together with the organic solvent.

  Thereby, the coating film which is a hardened | cured material of a coating composition is obtained.

  The pencil hardness of the coating film is, for example, 2H or more, preferably 4H or more. The pencil hardness is measured in accordance with, for example, JIS K 5600-5-4 (1999).

  The thickness of a coating film is 20 micrometers or more, for example, Preferably, it is 30 micrometers or more, for example, is 80 micrometers or less, Preferably, it is 60 micrometers or less.

  The coating composition contains a first oligomer, a second oligomer, a catalyst and an organic solvent, and the ratio of the total amount of the first oligomer and the second oligomer is 20% by mass or more. The catalyst is a metal alkoxide, a metal It is at least one selected from the group consisting of chelate compounds and metal carboxylates, and the vapor pressure of the organic solvent at 20 ° C. is 1 kPa or more. Therefore, the coating composition can be cured at room temperature. As a result, this coating composition is suitably used for applications that do not require heat treatment.

The coating composition contains a silicone oil, and the kinematic viscosity at 25 ° C. of the silicone oil is 100 mm ² / s or more. Therefore, the coating film which is a cured product of the coating composition is excellent in non-stickiness before and after rubbing.

  Furthermore, in the coating composition, since the ratio of the first oligomer to the second oligomer is 0.15 or more and 10 or less, the non-adhesiveness after the coating film is rubbed is excellent.

  Moreover, in the coating composition, the ratio of the total amount of a 1st oligomer and a 2nd oligomer is 50 mass% or less. Therefore, the coating composition is excellent in application workability. As a result, the coating film that is a cured product of the coating composition is excellent in appearance.

  Moreover, if an organic solvent is an alcohol solvent, it can suppress that a 1st oligomer and a 2nd oligomer carry out a condensation reaction, and produce | generates alcohol. That is, the reaction of the first oligomer and the second oligomer during storage of the coating composition (particularly, the silicone composition in the two-component curable composition) can be suppressed. Therefore, this coating composition (specifically, a silicone composition) is excellent in storage stability.

  In this coating composition, if the ratio of the organic solvent to the total amount of 100 parts by mass of the first oligomer, the second oligomer, and the silicone oil is 40 parts by mass or more and 300 parts by mass or less, the handling of the coating composition is performed. In addition to being excellent in properties, it is possible to suppress the generation of uneven coating thickness due to excessively rapid drying after coating, while suppressing an excessive decrease in yield.

  In this coating composition, if the ratio of the catalyst to the total amount of 100 parts by mass of the first oligomer and the second oligomer is 2 parts by mass or more and 55 parts by mass or less, the first oligomer and the second oligomer are at room temperature. Can be quickly cured to form a coating film at room temperature.

[Modification]
Also according to the modified example, the same operational effects as the above-described coating composition can be obtained.

  In the above description, the coating composition is prepared as a two-component curable composition. However, for example, the coating composition can be prepared as a one-component curable composition.

  Specifically, the first oligomer, the second oligomer, the silicone oil, the catalyst, and the organic solvent are blended in a state where there is no moisture (humidity) in the air. Specifically, the above-described components are blended and mixed in an inert gas atmosphere such as nitrogen and sealed in a container. Then, at the application site immediately before use, the container is opened and the coating composition is applied to the object. Even with this one-component curable composition, the same effects as the two-component curable composition can be obtained.

  Moreover, although this coating composition is a room temperature curing type, if necessary, it can be heated after room temperature curing (further heat curing), or can be heat cured instead of room temperature curing.

  In the heating, for example, a known temperature condition such as heating at 50 ° C. or higher is employed. The hardness of the coating film can be further improved by the heating described above.

  Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples. In addition, this invention is not limited to an Example and a comparative example at all. In addition, specific numerical values such as ratios (mixing ratios, content ratios), physical property values, and parameters used in the following descriptions are the ratios corresponding to those described in the “Mode for Carrying Out the Invention” above. Upper limit values (numerical values defined as “less than” or “less than”) or lower limit values (values defined as “greater than” or “exceeded”) such as (mixing ratio, content ratio), physical property values, parameters, etc. ) Can be substituted. In the following description, “part” and “%” are based on mass unless otherwise specified.

First, each component used in each example and each comparative example is described below.
X-40-9250: methyl silicone alkoxy oligomer (first oligomer) in which b is 8, c is 4, and d is 4 in formula (3), manufactured by Shin-Etsu Chemical Co., Ltd. KR-500: formula (6 ), Methyl-based silicone alkoxy oligomer (second oligomer) in which g is 10 and h is 4, manufactured by Shin-Etsu Chemical Co., Ltd. KF-96-10cs: polydimethylsiloxane, kinematic viscosity (25 ° C.): 10 mm ² / s KF-96-50cs: Polydimethylsiloxane, kinematic viscosity (25 ° C.): 50 mm ² / s, Shin-Etsu Chemical Co., Ltd. KF-96-100 cs: Polydimethylsiloxane, kinematic viscosity (25 ° C. ): 100mm ² / s, Shin-Etsu chemical Co., Ltd. · KF-96-1000cs: polydimethylsiloxane, kinematic viscosity ^{(25 ℃): 1,000mm 2 /} s, Shin-Etsu chemical Co. Company Ltd. · KF-96-1 ten thousand cs: polydimethylsiloxane, kinematic viscosity ^{(25 ℃): 10,000mm 2 /} s, Shin-Etsu Chemical Co., Ltd. · KF-96-10 ten thousand cs: polydimethylsiloxane, kinematic viscosity ( 25 ° C.): 100,000 mm ² / s, manufactured by Shin-Etsu Chemical Co., Ltd., KF-96-500,000 cs: polydimethylsiloxane, kinematic viscosity (25 ° C.): 500,000 mm ² / s, manufactured by Shin-Etsu Chemical Co., Ltd., KF -96-1 million cs: polydimethylsiloxane, kinematic viscosity (25 ° C.): 1,000,000 mm ² / s, manufactured by Shin-Etsu Chemical Co., Ltd. D-25: titanium (IV) tetra n-butoxide, Shin-Etsu Chemical Co., Ltd. -Titanium (IV) tetraisopropoxide, manufactured by Tokyo Chemical Industry Co., Ltd.-Titanium (IV) tetraethoxide, manufactured by Tokyo Chemical Industry Co., Ltd.-Aluminum (III) tri-sec-butoxy , Manufactured by Tokyo Chemical Industry Co., Ltd., aluminum (III) triisopropoxide, manufactured by Tokyo Chemical Industry Co., Ltd., aluminum (III) triethoxide, manufactured by Tokyo Chemical Industry Co., Ltd., zirconium (IV) tetra n-butoxide (approximately 80% 1-butanol solution) ), Manufactured by Tokyo Chemical Industry Co., Ltd., Tris (2,4-pentanedionato) aluminum (III), manufactured by Tokyo Chemical Industry Co., Ltd., tetrakis (2,4-pentanedionato) titanium (IV) (63% isopropyl alcohol solution) , Tokyo Chemical Industry Co., Ltd., bis (2,4-pentanedionato) bis (2-propanolate) titanium (IV) (75% isopropyl alcohol solution), Tokyo Chemical Industry Co., Ltd., tetrakis (2,4-pentanedionato ) Zirconium (IV), manufactured by Tokyo Chemical Industry Co., Ltd., bis (2-ethylhexanoic acid) zinc (II) (80 quality) % Diethylene glycol monomethyl ether solution), manufactured by Wako Pure Chemical Industries, Ltd., tris (2-ethylhexanoic acid) iron (III) (50% by mass mineral spirit solution), manufactured by Wako Pure Chemical Industries, Ltd., bis (2-ethylhexanoic acid) Cobalt (II) (65% by mass mineral spirit solution), manufactured by Nacalai Tesque, bis (2-ethylhexanoic acid) manganese (II) (50% by mass mineral spirit solution), manufactured by Wako Pure Chemical Industries, Ltd., methanol: 20 ° C. Vapor pressure at 13.3 kPa
Ethanol: vapor pressure 6kPa at 20 ° C
2-propanol: vapor pressure 4 kPa at 20 ° C
・ Cyclohexane: vapor pressure at 20 ° C. 10.6 kPa
Acetone: vapor pressure at 20 ° C. 24.7 kPa
Diethylene glycol dimethyl ether: vapor pressure 0.4 kPa at 20 ° C
Tripropylene glycol monomethyl ether: vapor pressure at 20 ° C. 0.004 kPa
Propylene glycol: vapor pressure at 20 ° C. 0.01 kPa
Water: vapor pressure 2.3 kPa at 20 ° C
Example 1
In a 200 ml glass container, 4.3 g of X-40-9250, 17.1 g of KR-500, 1.1 g of KF-96-1000cs, 67.5 g of 2-propanol, 10.0 g of D-25 The mixture was stirred for 20 minutes using a magnetic stirrer to prepare a coating composition (one-component curable composition).

  Separately, a flat test piece (thickness 1 mm, width 60 mm, length 90 mm, material A5052 aluminum alloy) as an object was subjected to solvent degreasing treatment with toluene, and then shot blasted using # 80 alumina particles. The coating composition was applied to the flat test piece by air spray and allowed to stand in an atmosphere of a temperature of 23 ° C. and a humidity of 40% for 18 hours to prepare a coating film.

(Example 2) to (Example 47) and (Comparative Example 1) to (Comparative Example 17)
A coating composition was prepared in the same manner as in Example 1 except that each component in each coating composition was changed according to Tables 1 to 6, and then a coating film was prepared.

(Evaluation of coating film)
The following items were evaluated about the coating film of each Example and each comparative example. The results are shown in Tables 1-6.

[appearance]
The coating film was visually observed, and the appearance (smoothness) of the coating film was evaluated according to the following criteria.

When fine holes were formed on the coating film when visually observed, the size of the holes was further measured with a digital microscope.
A: The surface of the coating film was smooth. The hole could not be confirmed visually.
B: Although there was no unevenness | corrugation on the surface of a coating film, there existed the hole (diameter 100 micrometers or more) which can be confirmed visually.
C: The surface of the coating film was uneven.
D: There were peeling and a crack in the coating film.

[Non-adhesive (peelable)]
(I) Peel strength of coating film before sliding test The non-adhesiveness (peelability) of the coating film was evaluated according to the 180-degree peeling method (JIS Z 0237: 2009, Method 4).

That is, first, an adhesive of Nichiban's cello tape (registered trademark) product number CT405AP-18 (width 18 mm) is adhered (pressure-sensitive adhesive), and then the cello tape (distance 80 mm) is applied from the coating film at a speed of 300 mm / min. Then, it was peeled off at a peeling distance of 80 mm. And the non-adhesiveness (peelability (easy peelability)) of the coating film was evaluated as peel strength.
(Ii) Peeling strength of coating film after sliding test Using a RUBING TESTER manufactured by Ohira Rika Kogyo Co., Ltd., wool felt was pressed against the coating film with a load of 1 kg / cm ² to conduct a sliding test. Specifically, the peel strength of the coating film after 5,000 slides was measured according to the 180-degree peeling method described above.

[Pencil hardness]
The hardness of the coating film was evaluated in accordance with the pencil hardness method (JIS K-5600-5-4 (1999)).

  First, using a tribogear TYPE 38 manufactured by Shinto Kagaku Co., Ltd., a vertical load of 750 g was applied to the pencil lead, and the pencil lead was set to contact the coating film at 45 degrees. Thereafter, the pencil was moved on the coating film at a sweep speed of 1 mm / second and a sweep distance of 20 mm. The pencils used were Uni 6B-9H manufactured by Mitsubishi Pencil Co., Ltd., and the pencil hardness at which the coating film was not shaved after being moved on the coating film was measured.

[Storage stability]
Under a room temperature (20 ° C.), a 100 ml glass bottle capable of being sealed was filled with 60 g of the coating composition (one-component curable composition) and then sealed.

  The state of the coating composition after standing for 4 weeks in a 40 ° C. atmosphere in a sealed glass bottle was evaluated according to the following four levels.

    A: The coating composition did not coagulate, aggregated, and did not thicken.

    B: The coating composition thickened more than at the start of storage.

    C: The coating composition partially aggregated and solidified.

    D: Half or more of the volume of the coating composition was aggregated and solidified.

Claims (5)

A first oligomer containing a dialkylsiloxane unit and an alkoxy group-containing siloxane unit containing an alkoxy group;
A second oligomer containing an alkoxy group-containing siloxane unit that does not contain a dialkylsiloxane unit and contains an alkoxy group;
With silicone oil,
A catalyst,
A coating composition containing an organic solvent,
The ratio of the total amount of the first oligomer and the second oligomer to the coating composition is 20% by mass or more and 50% by mass or less,
The ratio of the first oligomer to the second oligomer is 0.15 or more and 10 or less,
The kinematic viscosity at 25 ° C. of the silicone oil is 100 mm ² / s or more,
The catalyst is at least one selected from the group consisting of metal alkoxides, metal chelate compounds and metal carboxylates;
Vapor pressure at 20 ° C. of the organic solvent is state, and are more 1 kPa,
The ratio of the organic solvent to the total amount of 100 parts by mass of the first oligomer, the second oligomer, and the silicone oil is 40 parts by mass or more and 300 parts by mass or less.
Measured according to the description of JIS K 5600-5-4 (1999) of a coating film which is a cured product obtained by applying the coating composition, leaving it at 23 ° C. for 24 hours, and removing the organic solvent. It is the pencil hardness, characterized in der Rukoto than 2H, coating compositions.   The coating composition according to claim 1, wherein the organic solvent is an alcohol solvent. The paint composition according to claim 1 or 2 , wherein a ratio of the catalyst to a total amount of 100 parts by mass of the first oligomer and the second oligomer is 2 parts by mass or more and 55 parts by mass or less. object.   The coating composition according to any one of claims 1 to 3 is applied to an object, allowed to stand at 23 ° C for 24 hours, an organic solvent is removed, and a cured product of the coating composition. Form a coating,
  The pencil hardness measured according to the description of JIS K 5600-5-4 (1999) of the coating film is 2H or more.
A method for producing a coating film, comprising:   The coating composition is a room temperature curing type,
  The method for producing a coating film according to claim 4, wherein the coating composition is applied to the object in a site where heating is restricted.